Process for converting organic halides



Nov. 20, 1945. D. R. BLU-MER PROCESS FOR CONVERTING ORGANIC HALIDES Fild Feb. 10, 1942 EQUIPMENT SERVOIR PURIFICATION PREHEATEEO TAR TRAP COOLER mwmmow RACKING- FURNACE HEAT EXCHANGER VAPORIZER PREHEATER INVENTOR R. BLUMER DONALD lav 24 Patented Nov. 20, 1945 OFFICE 2,389,231 PROCESS FOR CONVERTING ORGANIC HALIDES Donald R. Blumer, Bartlesville, kla.,

Phillips Petroleum .0

- Delaware assignor to ompany, a corporation of I Application February 10, 1942, Serial No. 430,288

provements in processes for dehydrohalogenation of halogenated hydrocarbons for production of unsaturated hydrocarbons or halogenated derivatives thereof and pertains more particularly to the production of aliphatic conjugated diolefins and halogenated derivatives thereof, such as; for example, chlorobutadiene. It is especially applicable to the production of 1,3-butadiene from 2,3-dihalobutane. More specifically, itrefers to effecting said dehydrohalogenation reactions in open tubes or vessels without use of added solid catalysts or other dehydrohalogenating agents known to the art but rather thermally under very carefully controlled operating conditions, the only catalytic effect, if any, being caused by the wall surface or reaction or decomposition products formed on the walls of the reaction vessel.

It has been previously shown that such dehydrohalogenation reactions may be effected by passing the vapors of the halogenated materials at elevated temperatures through reaction vessels filled with solid dehydrohalogenation catalysts such as the halides, particularly the chlorides and bromides, of the following elements:

aluminum, barium, cobalt, copper, iron (ferrous),

lead, and nickel. Other catalysts mentioned are:

alumina; borates; phosphates; silicates; silicon alloys such as ferro-silicon, manganese-silicon,

- or copper-silicon; platinum; non-volatile acids such as phosphoric and boric acids; and materials having large surface areas such as silica gel, bleaching agents, activated carbon, filler materials coated with lustrous carbon, and chamotte. These catalysts may be either used alone or supported on suitable carriers such as pumice, activated charcoal, or like materials.

It has been shown that steam, Water vapor, or ammonia are effective in catalyzing dehydrohalogenation reactions in the vapor phase at elevated temperatures either in the presence or absence of solid catalysts such as those listed above. In the case of water vapor or steam, it appears that the halides are hydrolyzed to hydroxy comr pounds which are then dehydrated to the corresponding unsaturated compounds. Also, it has been shown that such catalyzed. reactions may be carried outby passing the vapors num chloride and potassium chloride in equimolecular proportions is especially suitable since it has low melting point and low vapor pressure at the temperature of the process. Also, it has I 2 Claims. (or. 260-680) This invention relates to new and useful impounds over heated. anhydrous alkalies or oxy compoundsof metals of metallobasic character such as the following: soda lime, caustic lime, calcium hydroxide; potassium hydroxide, sodium hydroxide, carbonates such as potassium carbonate,.lead oxide, magnesia, titanium dioxide, and other titanium oxides. In some cases in which the halogen is loosely bound, dehydrohalog'ena-.

ation may be efiected by heating or boiling the halogenated organic material with aqueous or alcoholic alkaline solutions such as those of potassium hydroxide or by treatment with amines I or organic bases such as aniline, quinoline, pyrof the halogenated compounds through molten metal halbeen shown that dehydrohalogenation may be effected by passing the halogenated organic comidine, or their methyl derivatives. It has also been shown that use of reduced pressure or inert diluents such as nitrogen, carbon dioxide, hydrogen, or the like favor such dehydrohalogenation reactions by reducing polymerization and other secondary reactions of the reaction products.

There are serious disadvantages inherent to the use of the above solid catalysts, such as the cost of the catalytic materials required and the expense of preparation of suitable catalysts, poor heat transfer through porous materials, poisoning of the catalysts by deposition of tar and other I decomposition products upon the catalytic surfaces, necessity for regeneration of the catalysts, clogging of the reaction vessels with tar and coke and necessity for cleaning out clogged catalyst beds. With the use of steam or water vaporin carrying out such reactions, the combination of Water vapor and hydrogen halide vapors and also aqueous hydrogen halide condensates which form' present serious corrosion difliculties which require'the use of very expensivecorrosion resistant alloys, refractories, or glass for construction purposes and also result in high maintenance costs. When ammonia is used for'dehydrohalogenation at elevated temperatures, there is considerable loss of this relatively expensive material because of decomposition to nitrogen and hydrogen. With molten metal halide baths difllculties are encountered because of sublimation of the salts and condensation in cooler parts of the reaction system. When dehydrohalogenation is effected by means of alkalies or oxy compounds of metals of metallobasic character the hydrogen halide liberated is fixed by formation of metal halides from which it is ordinarily very difiicult to recover the halogens for reuse in the process except by electrolysis, which requires very cheap electrical power in orde to have an economically feasibl process. Similary, when ammonia or the organic bases such as aniline, quinoline, pyridine, or their methyl derivatives are used for effecting dehydrohalogenation reactions, recovery of the hydrogen halides therefrom for reuse of both the acid andybasic constituents in the process is extremely difficult.

Th o j ct of this invention is to eliminate to as great an extent as possible the difllculties enumerated above which are encountered in effecting dehydrohalogenation reactions by known procedures. In addition, it is the purpose of this invention to secure additional advantages inherent in this improved process, which are as follows: By theuse of externally heated tubes of small diameter or chambers wherein the distance between the heated walls is small, it is possible to secure much better transfer of heat from the walls tothevapors of the halogenated organic compound for effecting endothermic dehydrohalogenation reactions than is-possible when heat transfer has to be effected through a relatively th.ck bed of porous solid catalyst. By passing the vapors through the heated reaction chamber rapidly enough, it ispossible to secure a high degree of dehydrohalogenation and yetkeep polymerization, decomposition, and other secondary reactions of the reaction products negligible so that there is very little tendency. for tarry or carbonaceous layers to deposit upon the walls of the reaction vessel, which deposits interfere with heat transfer and "may even result in plugging of the reaction vessel. With open tubes or reaction chambers such as are used in this process any tarry or carbonaceous layers which deposit upon the walls of the reaction vessels can be readily burned ofi or, if the vessel should clog completely, it can be cleaned out more readily than is the case if it is filled with solid catalysts which have become coked up.

V This invention is applicable to the dehydrogenation of halogenated hydrocarbons generally to produce unsaturated hydrocarbons and halogenated derivatives thereof. More particularly, it may be used for. dehydrohalogenating monohalogenated alkanes to oletlns, dihalogenated alkanes and/or monohalogenated alkenes to diolefins, trihalogenated alkanes and/or dihalogenated alkenes to monohalogenated dioleflns, and similar reactions. It can also be used for dehydrohalogenating dihalogenated alkanes to monohalogenated alkenes and for similar con- The process of the invention consists versions. of passing the vaporized halogenated hydrocarbons through a suitable corrosion-resistant reaction tube or chamber, which is heated externally or otherwise to a temperature sufliciently high to cause substantial evolution of hydrogen halide but not high enough to cause serious decomposition, polymerization, or other secondary reactions of the unsaturatedreaction products.

Temperatures required for such dehydrohalogenaticn reactions ordinarily lie within the following ranges: 250-750 C. for halogenated butanes, 250-650 C. -for halogenated pentanes, 250-600 C. for halogenated hexanes, and somewhat lower temperatures for the halogenated derivatives of the heptanes and .higher hydrocarbons. The total pressure is usually substantially atmospheric but may range from about 0.02 to 2 atmospheres. If the pressure of the material being decomposed is reduced below atmospheric or its partial pressure is reduced by dilution with inert diluents, lower temperature can be used to effect the same conversion that is obtained at atmospheric pressure with less loss of material due to decomposition, polymerization, and other secondary reactions of the initial products formed.

The contact time with the heated reaction space must'be carefully controlled to avoid such secondary reactions which result in loss of product. Ordinarily, this contact time is a few tenths rates the walls of the reaction vessel are swept freer of carbonaceous or other decomposition organic halide and it also products which tend to build up on the walls of the vessel and clog the passages at lower gas velocities. Rapid cooling of the efiluent gases'and separationof the unsaturated products from the hydrogen halide are effective in preventing back reactions and other secondary reactions which are likely to occur, particularly at higher temperatures.

This invention is best described by reference to the accompanying drawing, wherein the essential operations of the process are illustrated. The liquid organic halide feed stock which is to be dehydrohalog'enated is introduced into the reaction system through line I into circulating pump 2 by means of which" it is forced through coil'3 of the heat interchanger 4. Part of the heat available from the efiiuent from the dehydrohalogenation step, is utilized in heat interchanger 4 to preheat the feed stock, which then flows through line 6 into the vaporizer coil or chamber 1 of the vapor- -izer-preheater 8, wherein it is completely vaporized. At point In the vaporized organic halides may be mixed with inert diluents, if desirable, which have likewise been preheated by passage through the coil or chamber 9 of the vaporizerpreheater 8, which may preferably be heated by combustion of natural gas or refinery waste gases or in any other suitable way. The mixing of the organic halides with the inert diluents at the point H) may be eifected in a special mixing chamber or merely by depending upon the high velocity of the vapors flowing through the lines to cause suflicient agitation for-adequate mixing.

Inert diluents which may be used are nitrogen, carbon dioxide, hydrogen or any other gas which does not react to any appreciable extent with the products of the dehydrohalogenation reaction under the operating conditions of the process. Addition of such inert diluent is not necessary, al-

though it does permit dehydrohalogenation at lower temperatures of the temperature range required for a given organic halide with greater decomposition than would occur with undiluted tends to reduce polymerization, decomposition, and other secondary reactions of the reaction products since the partial pressure of these constituents is reduced. This is particularly desirable in the case of C5, Ca. and heavier halides, in which cases it is often -de sirable to use sufllcient inert diluent that the partial pressure of the organic halide lies within the range, 1550 mm. Hg. Complications are introduced by using such great quantities of diluent, however, such as difliculty in extraction of reac tion products from the diluted efiluents and also additional heat and heat transfer requirements for the larger volumes of vapor to be treated. It is best to keep the amount of diluent to the minimum required to prevent tar and coke formation and undesirable secondary reactions and in those cases where it is possible to operate satisfac torily without the use of a diluent, it is desirable to do so. The same efiect can be accomplished by the use of reduced pressure for the dehydrohalogenation step; however, production of the required reduced pressure is ordinarily impractical because of ,the corrosive nature of the 'eflluents, difficulty of recovering th gaseous products and undecomposed halides therefrom, and pumping and refrigeration costs involved.

The mixture of organic halide vapors with the' metal, or refractory material capable of withstanding corrosion by the hydrogen halide and other reaction products generated. General conditions of temperature, contact time, and pressure required for efiecting such reactions have been disclosed hereinabove. Special; conditions for given halogenated hydrocarbonsto give optimum yields of desired productsmay readily be determined by those skilled in'the art. Specific conditions for conversion of 2,3-dichlorobutane principally to 1,3-butadiene are revealed in the example below. However, it must be stressed that application of this process is not limited to this starting material and final product.

The effluents from reactor l I then pass through the cooling coil of the heat interchanger 4, wherein they are sufiiciently' cooled so that tar and other heavy polymerization products formed condense and flow'into tar trap l3 from which they may be removed assrequired through line H. The uncondensed vapors are cooled still further in the cooling coil- [5 of cooler I 6, whence they flow into fractionator l1, which represents a series of fractionators or fractionators and other extractors or scrubbers suitable for eparation of the various constituents or fractions of these constituents from the ellluent from the dehydrohalo-' genation step so that these various materials may be separately treated or recycled to the process in any desired proportions as required.

The treatment of these various constituents of i the eilluent may be illustrated by a description of the processing of the effluent from the dehydrohalogenation of 2,3-dichlorobutane; however, it must be understood that the same general procedure may be applied to the efiluents from the dehydrohalogenation of other organic halides. In the first step, the hydrogen chloride (B. P., -83.1 ratedby means of fractionation or a scrubbing operation from the higher boiling constituents and flow through line I8 to supplementary equipment for separating the inert diluent from. the hydrogen halide. Use of refrigeration is required for separation of the hydrogen halide and inert diluent from the unsaturated C4 hydrocarbons in this fractionationstep, particularly if it is conducted at atmospheric pressure, which is desirable to prevent reverse and other undesirable secondary reactions. eration may be secured at low cost by utilizing that produced by any vaporization of propane. butane, or othersuitable liquefied hydrocarbons required in any of the refinery processes.

A second fraction boiling in the range, to +5 C., is separated and leaves through line l9.

C.) and inert diluent, if present, are sepa- I (iii In many cases,this refrig-- This fraction consists principally of 1,3-butadiene .(B. P., 4.5 C.) but may contain traces of 1- butene (B. P., 6.3 C.-), 2-butene (B. P., +0.9 to +3.6" 0.), isobutene (B. P., -7.1 C.), n-butane (B. P., -05 c.), \11.8 C.). This fraction passes through lines 19 and 3| into the purification equipment, wherein the 1,3-butadiene is separated in pure form from the impurities by means of suitable solvent extraction or chemical purification processes, and the mixture of parafilns and o'lefins recovered is recycled back to the refinery for further processing or is utilized in any other way which may be desirable. The purified 1,3-butadiene passes through line 2| to storage.

A third fraction boiling in the range, 5 to 35 C., is separated in fractionator l1 and leaves through line 22, passing into the storage reservoir 23. This fraction consists principally of 1,2-butadiene (B. P., 10.3 C.) and may contain small amounts of l-butyne, (B. P., 8.8 C.), 2-butyne (B.-P., 27.2 C.), and possibly traces of vinylacetylene (B. P., 5. 1 C.), and biacetylene (B. P., 9.8 C.). This fraction may be recycled by means of pump 24 4 back to the dehydrohalogen'ation step in any desired proportions through valve 25A and line 25, valve 26A being closed. By recycling this material, it may be used to repress the equilibrium reactions wherein these productsare formed or these products maybe partially isomerized to the more desirable LB-bu-tadiene. However; this fraction is preferably treated separately to isomerize the unsaturated hydrocarbons contained therein as completely as possible to 1,3-butadiene since by recycling the material back to'the dehydrohalogenation step, part of it is wasted in decomposition, polymerization, and other secondary reactions. In isomerizing' these unsaturated hydrocarbons separately, they are forced by means of pump 24 through line 26, valve 25A being closed,' into the preheater and isomerization reaction chamber 21 which is heated in fur nace 28, which may be gas fired or otherwise heated. The efiluent from the isomerization reac-. tion chamber 21 passes through line 29 into fractionator 30, wherein the 1,3-butadiene formed is' separated from the higher boiling constituents and passes off through line 3|, into the purification equipment 20, where the 1,3-butadiene is separated from contaminants, as was hereinabove described, and passes through line 2| to storage. The contaminants are recycled back to the refinery for further processing or are utilized in any other way which may be desirable. The unsaturated hydrocarbons boiling in the range, 5 to 35" C., are separated in fractionat-or 30 and pass through line 32 to pump 24, which recycles them through the isomerization step. Any polymers or heavier hydrocarbons formed in the process are-removed from fractionator 3'0 through line 33, depolymerized and recycled to the isomerization step or otherwise utilized as may be desirable.

The isomerization, of isomers of 1,3-butadiene .to 1,3-butadine may be efiected catalytically by means of processes which are known to the art. For example, Y. M. Slobodin, J. Gen. Chem. (U, S. S. R.), 5, 48-52 (1935); ibid, '7, 2376430 (1937); C. A. 29, 4732 (1935); ibid., 32. 2081 (1938), found that if these isomers of l,3-butadiene are passed at a temperature in the range, 205 to 330 a special grade of fullers earth obtained from the Floridin Company, which has been previously activated'at 325 C., they are isomerized to form 1,3-butadiene with appreciable conversion per and isobutane (B. P.,'

C., preferably at 275 C., over Floridin,

pass and very little dimerization or polymerization. Also, I. G. Farbenindustrie A.-G., British Patent 507,847 (1939); C. A., 34, 454 (1940) disalkali carbonates, phosphates and silicates, or

mixtures thereof. The walls of the reaction chamber may be coated with alkalies or alkaline earths. Diluents are preferably present. Among examples, ethylacetylene is led at 460 C. and 35 mm. mercury pressure through magnesium oxide. Since 1,2-butadiene is less stablethan 1,3-butadiene and tends to isomerize to the latter form under the conditions cited by Slobodin, it, is apparent that the catalysts and operating conditions cited in the above patent would accomplish the same result. Under the above reaction conditions, traces of vinylacetylene and biacetylene which may be present are polymerized and removed from the reaction system.

A fourth fraction boiling in the range, 35 to 95 (3., is separated in iractionator i1 and leaves through line 34, passing into the storage reservoir- 35. This fraction consists principally of 3-chlorol-butene (B. P., 64 C.), although small amounts of other isomers such as, for example, l-chloro- 2-butene (B. P., 84- C.) may be present. This fraction may be recycled by means of pump 36 back to the dehydrohalogenation step in any desired proportions through line 38 and line 25, valve 31A being closed, to be dehydrohalogenated further to produce 1,3-butadiene or its isomers.

I! desired, this fraction may bepassed by means of pump 38 through line 31, valve 38A being closed, into separate dehydrohalogenation equipment similar to that described herein under other operating conditions which are more favorable for dehydrohalogenation of these particular compounds. Likewise, this fraction may be taken off through line 31 and utilized for the production of other more valuable special products.

A fifth fraction boiling in the range, 95 to 165 C., is separated in fractionator l1 and leaves through line 39, passing into the storage reservoir 40. This fraction consists principally of 2,3-dichlorobutane (B. P., 114-120 C.), but may contain small amounts of other diehlorobutane isomers having boiling points lying within the range, 102 to 163 C. This fraction may be recycled by means of pump 41 back to the dehydroh'alogenation step in any desired proportions through line 43 and line 25, valve A being closed, to be dehydrohalogenated further to produce, 1,3-butadiene or its isomers. I! desired, this fraction may be passed by means of pump 4| through line 42, valve 43A being closed, to additional fractionating equipment in which this fraction may be broken up into closer boiling cuts, the 2,3-dichlorobutane being recycled back to the dehydrohalogenation equipment and the other dichlcrobutane isomers being dehydrohalogenate'd separately in equipment similar to that previously described but maintained at other operat- I ing conditions more favorable for their dehydrohalogenation. Likewise, some of these dichlorobutane isomers may be recovered and utilized for the production or other more valuable special products.

A sixth fraction boiling above 165 C. is separated in iractionator l1 and leaves through line 4|. This bottom fraction which consists of higher boilingpolymers and higher chlorides may diluent is used either directly or after regeneration of free halogen therefrom to halogenate organic compounds in order to produce the organic halides required for treatment in the dehydrohalogenation process. In either case, the hydrogen halide reoovered is treated for removal of organic halide or hydrocarbon vapors contained therein by means of adsorption on charcoal or other suitable adsorbent, absorption in heavy oil or other suitable'scrubbing solvent having very low vapor pressure, burning out and dehydration step, or other suitable means and the residue used for halogenation as indicated above. Free halogen may be regenerated from this hydrogen halide by means of the Deacon, electrolytic or other suitable processes for reuse in the process to carry out the required halogenation step.

The-separation of the hydrogen halide from the inert diluent is efiected by scrubbing the gas mixture with constant-boiling aqueous hydrogen halide solution in absorber 45, which is constructed of suitable corrosion-resistant materials. into is introduced from line 46 into the top of absorber 45, in which it flows downward countercurrent to the gas flow. The inert gas substantially freed of hydrogen halide flows from the absorber through line A! to a scrubber l8 containing soda lime, lime, or other alkaline material for removal of the remaining small amounts or hydrogen halide present. This step is unnecessary provided that the lines and other p ent through which the inert gas must flow back to the dehydrohalogenation step are constructed of materials which will resist corrosion by the small amount of hydrogen halide contained therein. The inert gas then passes through drier 49, containing anhydrous alumina or other suitable desiccant, which serves to dry the gas and reduce corrosion diiliculties due to moisture, particularly ifthe small amount or hydrogen halide present is not first removed in the alkali scrubber 48. The dry gas is then drawn into the circulating pump 50, whence it is pumped through line ii and preheater coil 9 in the vaporlzer-preheater 8. The heated inert gas is then mixed with the vapors of the organic halides at the point II, from which the vapors flow through the dehydrohalogenation reactor I I in the cracking furnace i2 and on around through the cycle.

The aqueous hydrogen halide solution which has become more concentrated in hydrogen halide by absorption of the gas in absorber l5 flows out or the absorber through line 52 into the flash drum 53, wherein it is heated by means of the heating coilil to regenerate the constant-boilin aqueous hydrogen halide solution and drive off the absorbedhydrogen halide through the drier 55, containing anhydrous alumina or other suitable desiccant tor drying the hydrogen halide before returning it through line 56 for reuse in the process for direct halogenation reactions or for regeneration of free halogen by the Deacon, electrolytic, or other suitable processes. This drying through 49 and 62 through 6|, as well as the end step is not absolutely necessary but eliminates of line I8 which leads into absorber 45, requires necessity for special corrosion-resistant materials special corrosion-resistant construction to with-- in line 56 and in much of the equipment beyond stand attack by the aqueous hydrogen halidesoluthis point. As was previously indicated, it is de- 5 tions. This equipment may be constructed of sirable to treat the" dried hydrogen halide gas for stoneware; refractories such as glazed fused aluremoval of organic halides or hydrocarbons bemina, fused silica, silicon carbide, or the like; .fore sending it on to the halogen regeneration carbon or graphite; glass or glass-lined or coated step. metal parts; metal parts lined or plated with tan- Th'e constant-boiling aqueous hydrogen halide 10 talum or precious metals such as platinum; or solution regenerated in the flash drum 53 leaves any other suitable material which will resist corthrough line 57, passing through cooler 58 into rosion by such acids. In the case of hydrofluoric reservoir 59, whence it flows through line 60 into acid solutions, glass, fused silica, or refractories circulating pump 6|, which returns it through containing silica which will be seriously attacked line 46 to the absorber 45. by the hydrofluoric acid must not be used for the The operation of this scrubbing process for re-'- construction of such equipment. moval of the hydrogen halide from the inert'gas The following example will serve to illustrate ever, the maximum I page 301. Upon reboiling the concentrated acid may be illustrated by the use of constant-boiling further the nature of this invention, which, howaqueous hydrogen chloride as the scrubbing agent i ever, is not confin'ed to the processing of this parfor removal of hydrogen chloride from such a ticularorganic dihalide toproducea diolefin. as mixture. Such a solution has a concentration EXAMPLE of 10.5 molar per cent or 19.2 weight percent hydrogen chloride and a boiling point of l09.'7 C. e -2:3dich,loromlta'ne was vaporized the at one atmosphere absolute pressure. The coh- Vapors. P 5 9 at atmospheric Pressure through centration of the hydrogen chloride solution may a m l -b r constructed of 1 Stainless be increased to about 42weight per cent'hydrogen s e i tee .n t n n proximately chrochloride at a. temperature.,: of-;about 23? C; and lm lImandBZI-nickel, such alloys being sold under partial pressure of 'h chloride oro'n'e ate. Waugh-t e n m s as Stainless R l Z mosphere or somewh "th H I Sterling'-Ni rosta, Duraloy 13-8, etc.) the tube besorption is. carried on j r .Tingiheated to a temperature of 600 C. and car which r fri tio rdinafllyjqhi ed' w; fully'controlledat this valu The vapors were p3jt, -;,t h ai b epassed through the tube at such a rate that the al a fuhctionbf thj pahiafpresSureof m. contact time in the heated zone was 0.22 second drogen chloride in the gas-mixture being scrubbed emllent' gases Were q i kly cooled and the so that for partial pressures; below atmospheric; I m Q of theemuent determined by fracthe maximum concentration attainable will be" Fionafion and other analytical methods- The less th th maximum a e" cited. ov r. products isolated from a run made under these scrubbingoperations carried out at'ordinarytem-j experimental con i ns nd y l a a ained peratures and a total pressure of one atmosphere are Summarized maths table, wherein the P for th pure hydrogen chloride The maximum 40 nets are listed in-the first column; the number concentration of acid that one may expect to of moles of each individual product obtained from t m may be determined from the partial pressure one-hundred moles of initial 2,3-dichlorobutane of hydrogen chloride in the gas mixture to be charge stock are listed in the second column; the scrubbed and data for the partial vapor pressure per Pass conversion dataexpressed in P cent of hydrogen chloride Vapor over t aqueous solw of theoretical and based on the initial 2,3-dit as functi of'its concentration and the chlorobutane charge stock, are listed in the third temperature of the scrubbing operation, These column; and e Per pass ultimate onverslon data are available in tables such as the one in the data expressed in per cent of theoretical and based international Critical Tables, McGraw-Hill upon the zfi-dicmorobutane completely destroyed Book Company In N Y k 192 VOL III, in the reaction are listed in the fourth column.

TABLE in the flash drum 53, ,hydrogen chloride which is Dehydrohalogenation data for 2,3-dichlor0butanc practically anhydrous is evolved and the constant boiling hydrogen chloride solution recovered.

- y, this recovered solution will have a Nfimbemf Per pas-s com concentration of 19 to 22 weight per t hydro- Products moxeshom g c g on percent or n h id depending upon how completely the e E f gggggg gg absorbed hydrogen chloride is recovered from the 1mm 0438011 solution. The hydrogen chloride may be recovstmyed) hydrogen halide solutions as a function of their ered from the concentrated solution by'means of CH4 2. 44 0.01 1. 157 reduced pressure with or without the application 0-045 of heat or by passing gas through the solution if 331 3% e it is found advantageous to do so. 3: 9: 77

Similarly, other available data regarding the z l 2312 2 boiling point and composition of constant-boiling Z3333: aqueous hydrogen halide solutions and partial mus 5M9 moo vapor pressures of hydrogen halide Over aqueous From the above data it can'be seen that the per .concentrations and temperature may utilized pass. theoretical conversion of the 2,3-dich10rohalides for reuse in the process.

but 13 to determine the operating conditions required am 0 butadlene and butadiene amounts to 33.4 and 3.8 per cent, res ectivel for separation of other hydrogen hahdes Srom the lower molecular weight hydrocarbo ns and inert gas diluent and recovery of pure hydrogen amounts to a total of 1.7 per cent; and to recov- I erable and reusable 3-chloro-1-butene and 2,3- The equipment indicated by the numbers 45 dichlorobutane amounts to a total of 61.1 per cent. Also, considering that the 3-chloro-1-butene and 2,3-dichlorobutane can be recovered and reused in the process to produce 'butadiene,

it is evident that the per pass theoretical ultimate conversion to 1,3-butadiene and 1,2-butadiene based upon the 2,3edichlorobutane which is completely destroyed or not reusable in the process, amounts to 85.8 and 9.8 per cent, respectively, and to lower molecular weight hydrocarbons and tars amounts to a total of 4.4 per cent. Considering that the 1,2-butadiene can be almost completely isomerized to 1,3-butadiene by the procedure described above, -it is evident that ultimate conversions of 2,3-dichlorobutane to 1,3-butadiene approaching 95.6 per cent of theoretical can be obtained by means of the dehydrohalogenation process described above.

It must be stressed that the application of this invention is not limited to the dehydrohalogenation of 2,3-dichlorobutane to butadiene as cited in the above example. For example, the invention may be used to produce the following dehydrohalogenation products: olefins-Irom monohalogenated alkanes containing two or more carbon atoms per molecule; diolefins, alkyl acetylenes,- or monohalogenated mono-olefins from dihalogenated alkanes containing three or more carbon atoms per molecule, whereas four or more carbon atoms per molecule are required for concues from trihalogenated alkanes containing four or more carbon atoms per'molecule; monohalogenated dioleflns, monohalogenated acetylenes,

'dihalogenated mono-olefins from trihalogenated alkanes containing three or more carbon atoms per molecule, while four or more carbon atoms per molecule are required for production of from suitable tetrahalogenated alkanes, trihalogenated mono-olefins, or dihalogenated dioleflns or alkynes containing four or more'carbon atoms per molecule; and to the production of diolefinic alkynes from corresponding halogenated derivatives having five or more carbon atoms per molecule. The invention should not be restricted otherwise than. as specified in the appended claims.

By open, as used'herei'n, is meant unpacked.

I claim:

1. A process for the production of 1,3-butadiene from 2,3-dichlorobutane which comprises passing 2,3-dichlorobutane in vaporized form through an unpacked reaction tube at a temperature within the range of approximately 250 to approximately 750 C. and a pressure of from approximately 0.02 to approximately 2 atmospheres, segregating from the eiiluent a 1,3-butadiene fraction, 9. fraction containing incompletely dehydrochlorinated products and a fraction comprising 1,2-butadiene and allnvlacetylenes having four carbon atoms in the molecule, subjecting said fraction containing 1,2-butadiene and alkylacetylenes to isomerization in the presence of an activated fullers earth to convert a substantial portion of the constituents thereof to 1,3-butadiene, and recycling the fraction containing incompletely dehydrochlorinated products together with fresh 2,3-dichlorobutane to the unpacked reaction tube.

2. A process for the production of 1,3-butadiene from 2,3-dichlorobutane which comprises passing 2,3-dichlorobutane in vaporized form through an unpacked reaction tube at approximately atmospheric pressure and at a tempera-.. ture of approximately 600 0., segregating from the efiluent a 1,3butadiene fraction, a fraction comprising a substantial Proportion of 1,2-butadiene, and a fraction containing incompletely -dehydrochlorinated products, subjecting said 'LZ-butadiene fraction to isomerization in'the presence of an activated fullers earth to convert the 1,2-butadiene to 1,3-butadiene, and recyclin the fraction containing incompletely dehydrochlorinated products together with fresh 2,3-dichlorobutane to the unpacked reaction tube,

DONALD R, BLUMER. 

